WO2006090688A1 - Polymerization catalyst composition and process for production of polymer - Google Patents

Abstract

A polymerization catalyst composition for a radical polymerizable monomer, comprising a transition metal-containing phosphazenium composition which is produced by mixing a phosphazenium compound represented by the general formula (1) below with a compound of a transition metal belonging to Groups 4 to 12 on the periodic table with an organic halogen compound: (1) wherein n is an integer of 1 or greater which represents the numbers of phosphazenium cations; Zn- represents an anion of an active hydrogen compound in the form that is induced by allowing to leave n protons from an active hydrogen compound having n active hydrogen atoms; a, b, c and d independently are an positive integer of 3 or smaller or 0, provided that all of a, b, c and d are not 0; and R1 to R24 independently represent a hydrocarbon group having 1 to 10 carbon atoms and R1 and R2, R3 to R4, R5 and R6, R7 and R8, R9 and R10, R11 and R12, R13 and R14, R15 and 16, R17 and R18, R19 and R20, R21 and R22, or R23 and R24 may together form a ring.

Description

 Specification

 Polymerization catalyst composition and method for producing polymer

 Technical field

 The present invention relates to a novel polymerization catalyst composition for a radically polymerizable monomer, a transition metal-containing phosphatase composition comprising the same, a method for producing a polymer using the polymerization catalyst composition, and a method for producing the same It relates to the resulting polymer. More specifically, phospha

Transition metal-containing phosphazeum composition obtained by mixing at least one kind of transition metal compound selected from group 4 to group 12 of the periodic table, the transition metal-containing phosphaze-group The present invention relates to a composition and a polymerization catalyst composition for radically polymerizable monomers containing an organic halide, a method for producing a polymer using the polymerization catalyst composition, and a polymer obtained by this method.

 Background art

 [0002] A large amount of research has been conducted for radical polymerization from old times. Among them, in recent years, new polymers (blocks) are produced by arbitrarily and precisely controlling the molecular weight of the obtained polymer to produce a polymer having a narrow molecular weight distribution, or by copolymerizing several monomers in various methods. The living radical polymerization method that can produce grafts, stars, polymer brushes, etc.) has attracted attention. Among them, Atom Transfer Radical Polymerization (ATRP) has been extensively studied because the polymer can be precisely controlled in various forms. For example, in JP-A 10-509475 (patent document 1), an organic halide is used as an initiator, and a transition metal halide such as copper halide is used as a catalyst, and coordination of the transition metal compound is further carried out. There is disclosed a method of polymerizing a radically polymerizable monomer by using viviridine as a molecule. However, this method uses an expensive ligand, and since this ligand requires three times the equivalent of a large amount with respect to the catalyst, it is a cost as a method of industrially producing a polymer. There was a drawback of becoming high.

On the other hand, JP-A-2002-540234 (patent document 2) discloses a ribing radical polymerization method which overcomes the above-mentioned drawbacks. That is, it is a method which does not use an expensive ligand. Specifically, using an organic halide product as an initiator, tetraptyal ammonium bromide is used. This is a method of polymerizing a radically polymerizable monomer by using a transition metal halide such as an aluminum salt such as doe and the like and a halogen iron as a catalyst composition. Although this method does not require the use of expensive ligands, it has a low reaction rate and is not an industrially advantageous process.

. Patent Document 2 also describes that addition of an expensive ligand (for example, N- (2-pyridylmethyl) methaimine etc.) is necessary to enhance the reaction rate. .

Further, JP-A 2000-355606 (Patent Document 3) and International Publication WO 02 Z 30995 pamphlet (Patent Document 4) disclose phosphaze-um which is one of constituent compounds of the polymerization catalyst composition of the present invention. Disclosed is a method for producing a polymer in which a polar unsaturated compound is オ ン -on polymerized in the presence of the compound. However, in general, ァ -on polymerization is disadvantageous in that it is susceptible to impurities such as water. Therefore, a catalyst and a polymerization method which can advance living radical polymerization at a high reaction rate which does not use an expensive ligand by using a radical polymerization method capable of polymerization even in the presence of water etc. Not found.

 Patent Document 1: Japanese Patent Application Publication No. 10-509475

 Patent Document 2: Japanese Patent Application Publication No. 2002-540234

 Patent Document 3: Japanese Patent Application Laid-Open No. 2000-355606

 Patent Document 4: International Publication WO02Z30995 Pamphlet

 Disclosure of the invention

 Problem that invention tries to solve

[0005] The first object of the present invention is an industrially inexpensive catalyst component which is excellent in living property and causes no particular problems in production and handling in radical polymerization, and radically polymerizable compound containing the catalyst component. It is an object of the present invention to provide a polymerization catalyst composition for monomers.

 A second object is to provide an effective and efficient method for producing a polymer by polymerizing a radically polymerizable monomer using the polymerization catalyst composition.

[0006] Furthermore, a third object is to provide a polymer obtained by using a polymerization catalyst composition and polymerizing radically polymerizable monomers.

 Means to solve the problem

As a result of intensive studies to achieve the above object, the present inventors have found that certain transition metals are The polymerization catalyst composition containing a genus-containing phosphazene composition shows high activity for the polymerization of a radically polymerizable monomer, the polymerization reaction of which has a living polymerization property, and the polymer obtained has a narrow molecular weight distribution It has been found that the composition is a very effective polymerization catalyst composition, and the present invention has been completed.

 That is, the transition metal-containing phosphate composition according to the present invention is a phosphazene compound represented by the following general formula (1) and periodic table group 4 to 12 represented by the following general formula (2) It is a composition obtained by mixing at least one transition metal compound whose power is also selected.

[Formula 1]

[Wherein, n is an integer of 1 or more and represents the number of phosphazeyuum cations, and Z ⁿ — is an active hydrogen compound having n active hydrogen atoms and n protons are released A, b, c and d are each a positive integer of 3 or less or 0, but not all 0 at the same time.

R ^1Q , R ¹ \ R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ² °, R ²¹ , R ²² , R ²³ , R ²⁴ are the same or different Represents a hydrocarbon group having 1 to 10 carbon atoms which is good. Also, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R 1 ^Q , R ¹¹ and R ¹² , R ¹³ and R ^W , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁹ and R ² °, R ²¹ and R ²² , and R ²³ and R ²⁴ may bond to each other to form a ring).

 [Chem. 2]

LpM ^{m +} (X ^r- ) „(2) [Wherein, L represents a neutral ligand, p represents the number of neutral ligands, and is an integer of 0 or 1 to 8. M is a group 4 to 12 of the periodic table. Group power also represents a transition metal to be selected, m represents a valence number of transition metal M, and is an integer of 1 to 8. X “represents an の -on of a form in which a proton in an active hydrogen compound is eliminated and derived. , Q represents the number of a-on and is an integer of 1 to 8. r represents the valence of an a and is an integer of 1 to 8. The relationship between m, r and q is m = It is represented by r x q.)

 The polymerization catalyst composition for a radically polymerizable monomer according to the present invention contains the above transition metal-containing phosphaz- um composition and an organic halide.

The method for producing a polymer according to the present invention is characterized by using the above polymerization catalyst composition for radically polymerizable monomers as a catalyst composition when polymerizing radically polymerizable monomers to produce a polymer. .

 The polymer according to the present invention is a polymer obtained by the method for producing a polymer described above. Effect of the invention

 By using the polymerization catalyst composition of the present invention, living radical polymerization of a radically polymerizable monomer can be carried out at a faster reaction rate and at a lower cost than conventional catalysts. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

 The transition metal-containing phosphate composition of the present invention can be obtained by mixing the phosphazium compound represented by the following general formula (1) and the transition metal compound represented by the following general formula (2). Also, the polymerization catalyst composition for radically polymerizable monomers of the present invention contains this transition metal-containing phosphaz- um composition and an initiator.

[Chem. 3] (1)

LpM ^m ) q (2)

[0016] << Phosphatase-um Compound >>

 The phosphaze-cum compound used in the present invention is a force represented by the limit structural formula of the formula (1) in which the positive charge of the phosphazeyuum cation is localized on the central phosphorus atom. It also includes compounds drawn by innumerable limit structural formulas, and in fact its positive charge is delocalized to the whole.

General Formula (1)

R ¹⁰ , R ^U , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ", R ¹⁸ , R ¹⁹ , R ² °, R ²¹ , R ²² , R ²³ , R ²⁴ are the same or different It represents a hydrocarbon group having 1 to 10 carbon atoms which is good.

 Examples of the above-mentioned hydrocarbon group include linear or branched alkyl groups having 1 to L carbon atoms such as methyl group, ethyl group, 2-butyl group, n-pentyl group and the like, for example, cyclohexyl group and the like. A cycloalkyl group having a carbon number of 3 to 10, for example, an alkenyl group having a carbon number of 2 to 10, such as a burle group and a probel group, for example, a carbon number of 3 to 10 such as a cycloalkyl group; And cycloalkenyl groups, for example, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms such as phenyl, naphthyl and hydroxyethyl groups.

In the general formula (1), R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ^{1 ()} , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁹ and R ² °, R ²¹ and R ²² , and R ²³ and R ²⁴ may combine with each other to form a ring structure good. Examples of the group forming a ring structure by bonding to a nitrogen atom include, for example, A C 2 -C 10 alkylene group such as a lene group, tetramethylene group, pentamethylene group, etc .: for example, a C 3 -C 10 cycloalkylene group such as a cyclohexylene group, eg a biphenyl group And the carbon number of 2 to 10 carbon atoms, for example, a carbon number of 3 to 10 carbon atoms such as a cycloalkylene group, for example, a carbon number such as a phenyl group and a naphthylene group Examples thereof include 10 to 10 arylene groups such as, for example, a C 8-10 aralkiren group such as phenylethylene group. Such a ring structure may be formed on all nitrogen atoms having ⁴ to ^{4 or} may be formed on a part of nitrogen atoms!, Or.

Furthermore, some of the hydrogen atoms of these hydrocarbon groups represented by Ri to R ²⁴ are attached to a group containing a heteroatom such as oxygen atom, nitrogen atom, sulfur atom, silicon atom or a halogen atom. It may be replaced.

Ri to R ²⁴ are preferably a linear alkyl group having 1 to 8 carbon atoms and a group forming a ring structure among these hydrocarbon groups, and more preferably a methyl group, an ethyl group, a propyl group, a ring structure And a tetramethylene group or a pentamethylene group when forming a group, more preferably a methyl group or a tetramethylene group. Most preferably, it is all basic methyl groups of Ri to R ²⁴ .

 [0020] In the general formula (1), a, b, c and d are each a positive integer of 3 or less or 0. All forces are not 0 simultaneously. a, b, c and d are preferably positive integers of 2 or less, and preferred combinations of a, b, c and d include one of a, b, c and d being 2 and the other three A combination in which one is 1 and a combination in which all of a, b, c and d are 1 is mentioned, and a particularly preferable combination is a combination in which all of a, b, c and d are 1.

 In the general formula (1), n represents the number of phosphazeum cations. n is an integer of 1 or more, preferably an integer of 1 to 8, and more preferably an integer of 1 to 3.

In the general formula (1), Z ⁿ — is an anion of an active hydrogen compound in a form in which n protons are eliminated and derived from an active hydrogen compound having n active hydrogen atoms. The er-on of the active hydrogen compound represented by Z ⁿ — is not particularly limited as long as it is an ion capable of forming an ion pair with phosphazeum thione. This Examples of the active hydrogen compound giving z ⁿ — such as the above include compounds having an active hydrogen atom on a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom, mineral acids, super strong acids and the like. Note that an active hydrogen atom bonded to a carbon atom is —COR R (R is a hydrogen atom or

 2

 Alkyl group), CN, -NO or-COR (where R is a hydrogen atom or an alkyl group)

 2

 It refers to a hydrogen atom bonded to a carbon atom to which an electron withdrawing group is bonded.

Among compounds leading to Z ⁿ —, as a compound having an active hydrogen atom on a carbon atom, for example, monocarboxylic acid esters having 3 to 20 carbon atoms, 2 to 4 carboxylic acid ester groups Carboxylic acid esters such as polyvalent carboxylic acid esters having 5 to 20 carbon atoms having a carbon number of 4 to 20 formyl monocarboxylic acid esters having 2 to 20 carbon atoms, and 2 carbon atoms having a carboxylic acid ester group Formyl carboxylic acid esters such as 6 to 20 formyl polyhydric carboxylic acid esters; keto monocarboxylic acid esters having 4 to 20 carbon atoms, and 7 to 20 carbon atoms having 2 to 4 carboxylic acid ester groups Ketocarboxylic acid esters such as keto-multivalent carboxylic acid esters; mono-tolyl compounds having 1 to 20 carbon atoms, and 2 tolyl compounds having 3 to 20 carbon atoms and having 2 to 4 cyano groups Type: 3 to 20 carbon atoms And ketones such as C 4-20 polyhydric ketones having 2 to 4 carboxyl groups; carbon number 1-tolyloxides; carbon number 1-tolylthiooxides etc. Can be mentioned.

Examples of the monocarboxylic acid ester having 3 to 20 carbon atoms include aliphatic monocarboxylic acid esters such as ethyl acetate, cyclohexyl propionate, isopropyl butyrate, and methyl isobutyrate; Alicyclic monocarboxylic acid esters such as isopropyl xanthcarboxylate, for example, aliphatic monocarboxylic acid esters containing an aromatic ring such as ethyl phenyl acetate, etc. may be mentioned. Examples of C 5-20 polyvalent carboxylic acid esters having 2 to 4 carboxylic acid ester groups include jetyl malonate, jetyl succinate, jetyl adipate, tetrakis (2-ethoxycarbo-lethyl). Aliphatic polyvalent carboxylic acid esters such as ethylenediamine, for example, alicyclic polyvalent carboxylic acid esters such as 1, 2- (dimethoxycarboyl) cyclohexane, for example, aroma such as jetyl phenothioate And aliphatic polyvalent carboxylic acid esters containing a ring.

Examples of formyl monocarboxylic acid esters having 4 to 20 carbon atoms include aliphatic formyl monocarboxylic acids such as methyl formyl acetate and 3-formyl propionic acid cyclohexyl. Acid esters such as fatty cyclic formyl monocarboxylic acid esters such as 2-formyl 1-cyclohexanecarboxylic acid ethyl and the like, for example formyl monocarboxylic acid esters containing an aromatic ring such as fluoroformyl acetic acid etc. Be Examples of the C6 to C20 formyl polyhydric carboxylic acid ester having 2 to 4 carboxylic acid ester groups include aliphatic formyl polyhydric carboxylic acid esters such as dimethyl formyl malonate; Alicyclic formyl polyhydric carboxylic acid esters such as 2- (dimethoxycarboyl) 1 formylcyclohexane, for example, formyl polyhydric carboxylic acid containing an aromatic ring such as 1 formyl 2-phenyl phthalic acid Esters etc. are mentioned.

 Examples of the ketomonocarboxylic acid ester having 4 to 20 carbon atoms include aliphatic ketomonocarboxylic acid esters such as ethyl acetate, acetyl acetate cyclopentyl, and methyl groupalamoyl acetate, for example, 2- (methoxycarbonyl) And cycloaliphatic keto monocarboxylic acid esters such as cyclohexanone, for example, keto monocarboxylic acid esters containing an aromatic ring such as benzyl ethyl acetate and the like. Examples of the keto-polyvalent carboxylic acid ester having 7 to 20 carbon atoms having 2 to 4 carboxylic acid ester groups include aliphatic keto-polyvalent carboxylic acid esters such as jetyl acetylsuccinate, for example, 2, 3 Alicyclic keto polyvalent carboxylic acid esters such as diethoxycarbocyclohexanone, for example, aliphatic keto polyvalent carboxylic acid esters containing an aromatic ring such as dimethyl 2-acetylene-3-phenyl succinate etc. Be

 Examples of the mono-tolyl group having 1 to 20 carbon atoms include aliphatic mono-tolyls such as hydrogen cyanide, acetonitrile, 2-cyanopropane, etc., and aliphatic mono-tolyls such as cyclohexyl-tolyl. For example, aliphatic mono-trils containing an aromatic ring such as phenylacetonitrile can be mentioned. Examples of C 3-20 polyvalent tolyl groups having 2 to 4 cyano groups include aliphatic polyvalent tolyls such as malono-tolyl, 1,3-dicyanopropane, adipotolyl, etc. And alicyclic polyvalent-tolyls such as 1, 2-disocyanocyclohexyl and the like, for example, aliphatic polyvalent ditolyls containing an aromatic ring such as ditolyl phenylsuccinate.

Examples of the monoketones having a carbon number of 3 to 20 include aliphatic ketones such as acetone and methyl ethyl ketone, for example, alicyclic ketones such as dicyclohexyl ketone and the like; Aliphatic ketones containing an aromatic ring such as acetone, for example, aromatic ketones such as acetophenone and isopropylphenyl ketone, etc. may be mentioned. Examples of polyvalent ketones having 2 to 4 carbon atoms and having 2 to 4 carbonyl groups include aliphatic polyvalent ketones such as 2,4 pentanedione, for example, 1,3 cyclohexanedione and the like. And cycloaliphatic polyhydric ketones such as polyhydric ketones containing an aromatic ring such as 1-phenyl 2, 4 pentanedione and the like. Examples of C 1-tolyloxides include hydrogenation-toluoxide. Examples of -tolylthiooxides having one carbon atom include hydrogenated-tolylthiooxide.

Among compounds leading to Z ⁿ —, examples of compounds having an active hydrogen atom on an oxygen atom include water, monocarboxylic acids having 1 to 20 carbon atoms, and carbon having 2 to 6 carboxyl groups. Carboxylic acids such as polybasic carboxylic acids having a prime number of 2 to 20; carbamic acids having a carbon number of 1 to 20; sulfonic acids having a carbon number of 1 to 20; monohydric alcohols having a carbon number of 1 to 20, 2 to 20 Alcohols such as polyhydric alcohols having 2 to 20 carbon atoms having 8 hydroxyl groups; phenolics such as phenols having 6 to 20 carbon atoms having 1 to 3 hydroxyl groups; saccharides or derivatives thereof ; Polyalkyleneoxides having active hydrogen at the terminal; and cyanates having 1 carbon atom.

 Examples of the monocarboxylic acids having 1 to 20 carbon atoms include aliphatic monocarboxylic acids such as formic acid, acetic acid, trifluoroacetic acid, stearic acid and oleic acid, for example, aromatic rings such as phenylacetic acid and the like. Aliphatic monocarboxylic acids including, for example, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, for example, aromatic monocarboxylic acids such as benzoic acid, 2-carboxynaphthalene and the like.

 Examples of polyvalent carboxylic acids having 2 to 20 carbon atoms having 2 to 6 carboxyl groups include aliphatic polyvalent carboxylic acids such as oxalic acid and malonic acid, for example, cyclohexane, 1, 1 Alicyclic polyvalent carboxylic acids such as 2-dicarboxylic acid, for example, polyvalent carboxylic acids containing an aromatic ring such as 2-phenyldisuccinate, for example, aromatic polyvalent carboxylic acids such as phthalic acid and trimellitic acid Can be mentioned.

Examples of C 1 -C 20 forceful rubamic acids include N, N jetyl carbamic acid, phenyl carnomic acid, N, N, dicarboxy-2, 4 toluene diamine, etc. Be Examples of the sulfonic acids having 1 to 20 carbon atoms include aliphatic sulfonic acids such as methanesulfonic acid, for example, aliphatics containing a heterocycle such as 2 morpholinoethane sulfonic acid and 3- (N morpholino) propane sulfonic acid. Sulfonic acids, for example, aromatic sulfonic acids such as benzenesulfonic acid, ト ル エ ン -toluenesulfonic acid, 4-nitrobenzenesulfonic acid, 4,4-biphenyl disulphonic acid, 2-naphthalenesulfonic acid, picrylsulfonic acid, etc. For example, heterocyclic sulfonic acids such as 3-pyridine sulfonic acid and the like can be mentioned.

Examples of monohydric alcohols having 1 to 20 carbon atoms include aliphatic monohydric alcohols such as methanol, allyl alcohol and crotyl alcohol, and alicyclic monohydric alcohols such as cyclopentanol. For example, aliphatic monohydric alcohols containing an aromatic ring such as benzyl alcohol and the like can be mentioned. Examples of C 2 to C 20 polyhydric alcohols having 2 to 8 hydroxyl groups include ethylene glycol, propylene glycol, glycol glycol, butanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol and the like. Aliphatic polyhydric alcohols, for example, alicyclic polyhydric alcohols such as 1,4-cyclohexanediol, for example, polyhydric alcohols containing an aromatic ring such as 1-phenyl-1,2-ethanediol Etc.

 Examples of the C 6-20 carbons having 1 to 3 hydroxyl groups include pheno mononore, creso mono nore, nitrophenol nore, cromophor fenole, naphtho nore, 9 fuenanthrole, 1 And monohydric phenols such as hydroxypyrene, for example, dihydric phenols such as catechol, dihydroxy naphthalene, bisphenol A and the like. Examples of the saccharides or derivatives thereof include saccharides such as glucose, sorbitol, dextrose, fructose, sucrose and the like, and derivatives thereof. Examples of polyalkylenoxides having active hydrogen at the end include polyethylene oxide, polypropylene oxide, copolymers thereof and the like and having 2 to 8 ends and having 1 to 8 hydroxyl groups at the ends. Polyalkylene oxides having an average molecular weight of 100 to 50000 and the like can be mentioned. Examples of cyanates having 1 carbon atom include hydrogenated cyanates.

Among the compounds leading to Z ⁿ —, as the active hydrogen compound having an active hydrogen atom on the nitrogen atom, for example, ammonia; C 1-20 primary amines, C 2-20 carbon atoms Secondary amines, C 2-20 polyhydric amines having 2 to 4 primary or secondary amino groups Saturated cyclic secondary amines having 4 to 20 carbon atoms, unsaturated cyclic secondary amines having 4 to 20 carbon atoms, 4 to 20 cyclic rings having 2 to 3 secondary amino groups Amines such as polyhydric amines; unsubstituted or N-monosubstituted acid amides having 2 to 20 carbon atoms, cyclic amides having 5 to 7-membered rings, dicarboxylic acids having 4 to 10 carbon atoms Imides; azides having 0 carbon atoms; isocyanides having 1 carbon atom, and the like.

Examples of the primary amines having 1 to 20 carbon atoms include aliphatic primary amines such as methylamine, ethylamine and propylamine, for example, alicyclic primary amines such as cyclohexylamine and the like, for example benzylamine, Aliphatic primary amines containing an aromatic ring such as phenylethylamine, for example, aromatic primary amines such as aromatic and toluidine, etc. may be mentioned.

 Examples of secondary amines having 2 to 20 carbon atoms include aliphatic secondary amines such as dimethylamine, methylamine and dipropylamine, for example, alicyclic secondary amines such as dicyclohexylamine and the like Examples thereof include aromatic secondary amines such as N-methyl phosphorus and diphenyl diamine. Examples of polyhydric amines having 2 to 20 carbon atoms having 2 to 4 primary or secondary amino groups include ethylenediamine, bis (2-aminoethyl) amine, hexamethylenediamine, tris (2) -Aminoethyl) amine, N, N, monodimethyl ethylene diamine, etc. may be mentioned.

 Examples of the saturated cyclic secondary amines having 4 to 20 carbon atoms include pyrrolidine, piperidine, morpholine and the like. Examples of unsaturated cyclic secondary amines having 4 to 20 carbon atoms include 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole, purine and the like. Examples of cyclic polyhydric amines having 4 to 20 carbon atoms containing 2 to 3 secondary amino groups include piperazin, 1,4,7-triazacyclononane and the like.

Examples of unsubstituted or N-monosubstituted acid amides having 2 to 20 carbon atoms include, for example, acetate amide, N-methylpropionamide, N-methylbenzoic acid amide, N-ethylstearic acid amide, etc. Can be mentioned. As 5- to 7-membered cyclic amides, for example, 2-pyrrolidone, _ε monoprotaxam, etc. may be mentioned.

Examples of imides of dicarboxylic acids having 4 to 10 carbon atoms include succinimide, and An acid imide, a phthalimide, etc. are mentioned. Examples of azides having 0 carbon atoms include hydrogenated azides and the like. Examples of isocyanides having one carbon atom include hydrogenated isocyanide and the like.

Among the compounds leading to Z ⁿ —, examples of the active hydrogen compound having an active hydrogen atom on a sulfur atom include sulfur hydrogen; monohydric alcohols having 1 to 20 carbon atoms, carbon atoms Thio alcohols such as 2 to 20 polyhydric alcohols; and thiophenols such as thiophenyl alcohol having 6 to 20 carbon atoms.

 Examples of monohydric thioalcohols having 1 to 20 carbon atoms include aliphatic monohydric thioalcohols such as methanethiol, ethanethiol and arylmerkabutane, and aliphatics containing an aromatic ring such as benzylmerkabutane 1 Thioalcohols, for example, cycloaliphatic monohydric alcohols such as cyclopentyl mercaptan and cyclohexyl mercaptan, etc. may be mentioned. Examples of polyhydric alcohols having 2 to 20 carbon atoms include 1,2-ethanediol, 1,3-propanedithiol, 1,2,3-propanetrithiol, 2,3 bis (mercaptomethyl) 1, and the like. 4 butane dithiol etc. are mentioned.

 Examples of C 6-20 thiophenols include monovalent thionols such as thiophenyl, thiocresol and thionaphthol, and dihydric thiophenols such as 1,2-benzenedithiol. .

Among the compounds leading to Z ⁿ —, mineral acids include, for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen halides such as hydrogen bromide, boric acid, phosphoric acid, phosphorous acid, hydrogen cyanide, thiocyanic acid Nitric acid, sulfuric acid, carbonic acid, perchloric acid and the like.

Among the compounds leading to Z ⁿ —, among the superacids, for example, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, trifluoromethanesulfonate, trifluoromethane, and the like. Sulfonimide, tris (trifluoromethanesulfonyl) methane and the like can be mentioned.

Among the active hydrogen compounds that lead to these Z ⁿ —, preferably, the active hydrogen atom is a mineral acid or an oxygen atom, a nitrogen atom, a sulfur atom, or a carbon atom to which an electron attractive group is bonded. It is an active hydrogen compound which it has, more preferably a mineral acid, still more preferably hydrogen chloride, hydrogen bromide or hydrogen iodide. << Compound of Transition Metal >>

 The transition metal compound selected from the group 4 to group 12 of the periodic table used in the present invention acts on the initiator used in the present invention to generate a radical, and is a transition metal capable of polymerizing a radically polymerizable monomer. It is a compound, The general formula is represented by Formula (2).

 [Formula 4]

LpM ^{m +} CX ^r- ) _q (2)

In the formula, L represents a neutral ligand, p represents the number of neutral ligands, and is an integer of 0 or 1 to 8. M represents a transition metal from which the periodic table group 4 to group 12 force is also selected, m represents the valence of the transition metal M, and is an integer of 1 to 8. X represents an a-on of a form in which a proton in an active hydrogen compound is eliminated and derived, q represents a number of a-on, and is an integer of 1 to 8. r is a valence of an electron And represents an integer of 1 to 8. The relationship between m, r and q is represented by m = r x q.

More specifically, the transition metal M is, for example, a group 4 metal such as titanium or zirconium, for example, a group 5 metal such as vanadium or niobium, for example, a group 6 metal such as chromium or molybdenum. For example, Group 7 metals such as manganese, for example, Group 8 metals such as iron and ruthenium, for example Group 9 metals such as cobalt, for example Group 10 metals such as nickel and palladium, for example copper Examples thereof include Group 11 metals, for example, Group 12 metals such as zinc.

 [0045] Of these transition metals, iron or copper more preferably selected from Group 8 or 11 transition metals, which are preferably Group 7 or 8, 9 or 10 or 11 metals of the periodic table. Most preferred is iron which is even more preferred.

Specifically, as the ァ -on X in the transition metal compound of the general formula (2), there may be mentioned 例 示 -on exemplified as the hydride (H ") and Z ⁿ in the general formula (1) .

Among these protons X ′, preferred are halogen ions, and more preferred are chloride ions, bromide ions and iodine ions. That is, among transition metal compounds used in the present invention, preferred are And transition metal halides, more preferably chlorides, bromides and iodides of transition metals.

The transition metal compound of the general formula (2) may have a neutral ligand L. Neutral ligand Examples of L include neutral ligands containing carbon atom, oxygen atom, nitrogen atom, sulfur atom, or phosphorus atom.

[0047] Examples of the neutral ligand L containing a carbon atom include carbon monoxide, C4-20 carbons, C6-20 aromatic hydrocarbons, and the like.

 Examples of the gens having 4 to 20 carbon atoms include, for example, gens such as cyclopentadiene, cycloactadiene, norbornadiene and the like. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include aromatic hydrocarbons such as benzene, naphthalene, pyrene and the like.

 [0048] Examples of the neutral ligand L containing an oxygen atom include water and ethers having 2 to 20 carbon atoms.

 Examples of the ether having 2 to 20 carbon atoms include aliphatic ethers such as dimethyl ether, dimethyl ether, ethyl ethyl ether, and the like; alicyclic resins such as tetrahydrofuran, 1,4-dioxane, dicyclohexyl ether, etc. Formula ethers include, for example, ethers containing an aromatic ring such as dibenzyl ether, and examples thereof include aromatic ethers such as diphenyl ether and naphthalene phenyl ether.

Examples of the neutral ligand L having a nitrogen atom include nitrogen molecule, ammonia, tertiary amines having 3 to 20 carbon atoms, and 6 to 6 carbon atoms having 2 to 4 tertiary amino groups. Examples include 50 polyvalent amines; aromatic amines having 5 to 30 carbon atoms.

Examples of tertiary amines having 3 to 20 carbon atoms include aliphatic tertiary amines such as trimethylamine and diisopropyl methylamine, and alicyclic tertiary amines such as N-methylbiperidine, such as Tertiary amines containing an aromatic ring such as til benzylamine and the like can be mentioned. Examples of C6 to C50 polyhydric amines having 2 to 4 tertiary amino groups include tetramethylethylenediamine, N, N, Ν ′, Ν ′ ′, Ν ′ ′-pentamethyl-ge Thilentriamine, Ν, Ν, Ν ', Ν', Ν ", Ν" Hexamethinoletriethylenetetramine, Ν, Ν, Ν ', Ν', Ν ", Ν" Hexakis [(2-η-butoxy Aliphatic polyhydric amines such as carbyl) ethyl] triethylene tetramine, for example, alicyclic polyvalent amines such as 1, 2-dipi- bendinoethane, such as 1,4- dibenzyl piperidine Tertiary polyhydric amines containing an aromatic ring may, for example, be mentioned. Examples of aromatic amines having 5 to 30 carbon atoms include pyridine and dipyridine And aromatic amines such as 2,2, -bipyridine, 2,2,1 [4,4,1 bis (5-nonenole)] bipyridine, quinoline, 1,10-phenanthrin and the like.

 Examples of the neutral ligand L having a sulfur atom include thioethers having 2 to 20 carbon atoms; and aromatic compounds containing a sulfur atom having 3 to 8 carbon atoms.

 Examples of thioethers having 2 to 20 carbon atoms include aliphatic thioethers such as dimethyl sulfide, for example, alicyclic thioethers such as tetrahydrothiopyran, for example, an aromatic ring such as dibenzyl sulfide. And thioethers containing Examples of the aromatic compounds containing a sulfur atom having 3 to 8 carbon atoms include aromatic compounds containing a sulfur atom such as thiophen, thiazol and thianaphthalene.

 Examples of the neutral ligand L having a phosphorus atom include phosphines having 3 to 30 carbon atoms. Examples of phosphines having 3 to 30 carbon atoms include aliphatic phosphines such as triethyl phosphine and tributoxy phosphine, for example, alicyclic phosphines such as 1-ethyl phosphinan, and examples thereof include triphenyl phosphine and the like And phosphines containing the aromatic ring of

M in the general formula (2) represents the valence of the transition metal M and is an integer of 1 to 8. p represents the number of neutral ligands L and is an integer of 0 or 1 to 8. r represents a valence number of "a-on X" and is an integer of 1 or more, preferably an integer of 1 to 8. In the transition metal compound of the general formula (2), the positive charge of the transition metal ion M ^{m +} and Since the sum of negative charges of “on X” is balanced, as a whole is electrically neutral, the relationship m = r × q holds between m, r and q. Also, q or p is When two or more, two or more ァ -on X 'or neutral ligands L may be identical or different, respectively!

 Furthermore, the transition metal compound of the general formula (2) is usually a mononuclear transition metal compound in which the central metal is one, and in some cases, has two or more same or different central metals. It may be a multinuclear transition metal compound. As the transition metal compound of the general formula (2), an isolated compound may be used or, for example, a compound containing a transition metal and a neutral ligand may be separately added to generate in the system! .

 [Organic Halide]

The organic halides used in the present invention can be prepared by using the polymerization catalyst composition of the present invention. It acts as an initiator when polymerizing a thermally polymerizable monomer. The organic halide is a compound containing at least one or more fluorine atom, chlorine atom, bromine atom or iodine atom in the organic compound.

 Specific examples of the organic halide include halogenated hydrocarbons, halogenated sulfonyls, halogenated carboxylic acid esters, halogenated ditolyls, halogenated ketones, and halogenated alcohols. , Halogenated ethers, Halogenated carboxylic acids, Halogenated aldehydes, Halogenated carboxylic acid halides, Halogenated powers Carboxylic acid anhydrides, Halogenated carboxylic acid amides, Halogenated carboxylic acid imides, Halogenation There may be mentioned humamines, halogenated phenols and the like.

 The halogenated hydrocarbons include, for example, aliphatic tetrasubstituted halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide, methane tetraiodide, and bromotrichloromethane, for example, chloroform, bromoform Aliphatic trisubstituted aromatic hydrocarbons such as iodoform and 1,1,1-tribromoethane, for example, aliphatic disubstituted halogenohydrocarbons such as dichloromethane, dibromomethane, joodemethane, and 1,1 dibromoethane For example, aliphatic 1-substituted halogenated hydrocarbons such as methyl bromide, methyl iodide, ethyl bromide, t-butyl bromide and the like, for example, alicyclic di-substituted such as 1, 1 di-bi mocyclohexane and the like Halogenated hydrocarbons such as, for example, 1-bromo 1-substituted halogen substituted hydrocarbons such as 1-methylcyclohexene, such as (1-chloroethyl) benzene, (1- Monosubstituted halogenohydrocarbons containing an aromatic ring such as lomocheyl) benzene, (1odoethyl) benzene, eg disubstituted halogenohydrocarbons containing an aromatic ring such as (1,1-dibromoethyl) benzene, eg And a, a, a, tri-substituted halogenated hydrocarbons containing an aromatic ring such as tribromotoluene.

Examples of halogenated sulfoles include trichloromethanesulfonyl chloride, trichloromethanesulfonyl bromide, trichloromethanesulfonyl iodide, dichloromethanesulfonyl bromide, chlorochlorosulfonyl bromide and the like. Alkyl halosulfonyls such as methanesulfonyl chloride, methanesulfonyl bromide, methane iodide iodide and the like, for example, aliphatic halogenated sulfonyls containing an aromatic ring such as benzyl chloro sulfone, such as salts And halogenated sulfones such as aromatic halogenated sulfols such as benzenesulfonyl. The halogenated carboxylic acid esters include, for example, methyl bromoacetate, methyl iodoacetate, methyl ethyl acetate, ethyl acetate bromoethyl acetate, ethyl acetate bromoacetic acid, ethyl diacetate, methyl dibromoacetate, ethyl 2-bromopropionate, 2-bromo- 2-Methylpropionate ethyl, trifluoroacetate butyrole, bromomalonate dithionol, dichloromalonic acid dimethinole, bromosuccinic acid ethinole, 2-chloro-3 bromosuccinic acid dibutynol, 1 chlorocyclohexahexanomethyl methyl ester, 3-bromo-monotetrahydropyranone 2-one And α-halogenated carboxylic acid esters containing an aliphatic, alicyclic or aromatic ring having a halogen group at the α-position, such as 3-chloro-one-tetrahydrofuran 2-one, bromo-phenyl acetate, etc., for example, 3-bromopropion Acidyl, 4 Halogenated carboxylic acids containing an aliphatic, alicyclic or aromatic ring having a halogen group other than α-position such as methyl chlorobutanoate, ethyl 3-bromocyclopentane carbonate, butyl 3-bromo-3-phenylpropionate, etc. Esters, for example, carboxylic acids containing an aliphatic, alicyclic or aromatic ring such as acetic acid (1-bromoethyl), propionic acid (2-chlorobutyl), cyclohexyl carboxylic acid (1 promoetyl), phenylacetic acid (1 promoetyl), etc. Acid haloesters etc. are mentioned.

Examples of the halogenated-tolyl compounds include, for example, bromoacetonitrile, bromochloroacetonitrile, 2-bromo-2-methylpropioditolyl, trichloroacetonitrile, 1-bromocyclohexyl oral carbocarbotriyl, 1 chlorocyclopentanecarbo Ex-halogenated-tolyls containing an aliphatic, alicyclic or aromatic ring having a halogen at the α position such as di-tolyl, bromo-phenyl-acetonitrile etc., for example, 3-bromopropio-tolyl, 4-chlorobutyl-tolyl, Examples thereof include aliphatic chloroaliphatic or aromatic ring-containing halogenated ditolyls having halogen other than α-position such as 3-chlorocyclohexancarboditril, 3bromo-2 phenylpropioditril and the like.

Examples of halogenated ketones include aliphatic halogenated ketones such as bromoacetone, 1,1-dichloroacetone, 1,1,1 tolyodoacetone, 1-bromo-4 chloro-2 butanone, and the like. —Acetyl-1-alicyclic halogenated ketones such as 1-bromocyclohexane, 2-chlorocyclohexanone, 3bromocyclopentanone and the like, for example, aromatic rings such as 2 chloroacetophenone, 4-bromo-3 phenylbutane 2 one and the like Aliphatic halogenated ketones and the like can be mentioned. The halogenated alcohols include, for example, aliphatic alcohols such as 2-necked ethanol and 1-bromobutanol, for example, alicyclic alcohols such as 2-chlorocyclohexanol and 1-bromocyclopentanol, and the like Examples thereof include halogenated alcohols containing an aromatic ring such as 2-bromo-2-fluoroethanol and 4-chloro-3-fluorobutane-1-ol.

 Examples of halogenated ethers include aliphatic halogenated ethers such as bis (2-chloroethyl) ether and 1-bromo 1-ethoxybutane, for example, 2-bromotetrahydrofuran, bis (2-chlorocyclohexyl) Alicyclic halogenated compounds such as ethers, for example, halogenated ethers containing an aromatic ring such as 1-bromo 3- (2-phenylethoxy) butane and 1-chloro-1-phenoxetane It can be mentioned.

 The halogenated carboxylic acids include, for example, aliphatic halogenated carboxylic acids such as 2 bromoacetic acid and 3 crocodile propionic acid, and examples of alicyclic carboxylic acids such as 2-chlorocyclohexane carboxylic acid and 1-bromocyclopentyl carboxylic acid Halogenated carboxylic acids of the formula, for example, halogenated carboxylic acids containing an aromatic ring such as 2-chlorophenylacetic acid, 3-bromo-2-phenylpropionic acid and the like can be mentioned.

 As the halogenated aldehyde, for example, aliphatic halogen aldehydes such as 2 chloroethanal and 6 bromohexanal, for example, alicyclic such as 1-chlorocyclohexane forcevalide, 2-bromocyclopentanecarbaldehyde and the like Halogenated aldehydes of the formula, for example, aldehydes containing an aromatic ring such as 2-phenyl-2-chloroacetaldehyde, 2-phenyl-3 bromopropion aldehyde and the like can be mentioned.

Examples of halogenated carboxylic acid halides include aliphatic halogenated carboxylic acid halides such as chloroacetyl chloride, 3bromopropioninorebromide, 2-bromo-2-methinolepropioninorebromide, and the like. For example, cycloaliphatic halogenated carboxylic acid halides such as 1-chlorocyclohexanecarbolide, 2bromocyclopentanecarbobromide etc., for example, 2-chloro-2-phenylacetic acid chloride, 3-chloro-2-phenyl Halogenation power containing an aromatic ring such as propionoyl bromide.

As the halogenated carboxylic acid anhydride, for example, 2-chloro-acetic anhydride, cro-acetic acid Aliphatic halogenated carboxylic acid anhydrides such as propionic acid anhydride, such as, for example, 1-chlorocyclohexanoic acid propionic acid anhydride, 2 chlorosuccinic acid anhydride, 3 bromo-1,2-cyclohexanedicarboxylic acid anhydride etc. Alicyclic halogenated carboxylic acid anhydrides, for example, halogenated carboxylic acid anhydrides containing an aromatic ring such as phenylacetic acid and crotonic acetic acid anhydride, and the like can be mentioned.

 Examples of halogenated carboxylic acid amides include aliphatic halogenated carboxylic acids such as chloroacetamide, 3-bromohexanamide, N-chloromethylacetamide, N, N-bis (2-bromoethyl) butanamide and the like. Amides such as, for example, cycloaliphatic halogenated carboxylic acid amides such as 1-chlorocyclohexanamide, 2-bromo-4-butanelatatum, N- (2-bromocyclohexyl) acetamide, such as 2-bromo-2-heterophthalamide, N- Examples thereof include halogenated carboxylic acid amides containing an aromatic ring such as (3 joodopropyl) 3-phenylpropanamide, N, N-diphenyl 3-chlorobutanamide and the like.

 Examples of the halogenated carboxylic acid imides include alicyclic chlorocarboxylic acid imides such as 3-chlorosuccinimide and 1-chloro-1,2-cyclohexanedicarboximide, and examples thereof include 3-bromo-, for example. 4) Halogenated carboxylic acid imides containing an aromatic ring such as phenyl succinimide, for example, aromatic halogenated carboxylic acid imides such as N- (3-chlorobutyl) phthalimide and the like.

Examples of halogenated amines include chloromethylamine, 2-bromoethamine, 3-hydroxypropylamine, ethylchloromethylamine, bis (3-chloropropyl) amine, and the like. Aliphatic halogenoamines such as tris (4-bromobutyl) amine, for example, 2-chlorohexyl hexylamine, bis (2-bromocyclohexyl) amine, N-methyl 2-chloropiperidine, 2-chlorocyclohexyldimethylamine Alicyclic halogenated amine such as 2-chloro pyrrolidine, 2-bromopiperidine, 2-chloro morpholine, 4-chloro pyrroline, for example, 1-bromo 1-phenylmethylamine, 1-chloro 1- A halogen halide containing an aromatic ring such as phenylethylamine, benzyl (3-bromopropyl) amine, and benzyl-bis (chloromethyl) amine Groups, for example, 2-chloromethyl adiphosphorus, N-chloromethyl aphosphorus, N- (2 bromoethyl) aphosphorus, N-methyl-N- (3 bromopropyl) a-phosphorus, 4 chloromethyl pyrrole, 3 bromo methyl indole, 2 Chloromethino recanoreva Aromatic halides such as azole, 2- (2-bromoethyl) imidazole, 3- (3-bromopropyl) pyrazole, 2-bromomethyl naphthyridine, 2-chloromethyl quinazoline, 2- iodomethyl pyrimidine, etc., for example, 1 Closed mouth ethylene diamine, bis (2-amino 1 chloroethy1) amine, 2-bromohexamethylene diamine, tris (2 amino ethyl) amine, N, N, N, N "N ,, pentakis (chloromethyl) diethylene Aliphatic halogenated polyhydric amines such as triamine, for example, cyclic fluoropolyamines such as 2 chloropiperazine, 2 bromo 1, 4 and 7 triaza cyclononane, and the like.

Examples of halogenated phenols include 2-chloromethylphenol, 4-bromomethyl 2-naphthol, 3-bromomethyl-4,4-biphenyldiol and the like.

 The organic halide of the present invention is not limited to low molecular weight organic halides, but may be halides of polymer compounds (polymers). For example, some of the inorganic compounds such as silica gel may be used. It may be a complex compound of an inorganic compound and an organic halide which is modified with an organic halide. As the halide of the polymer compound (polymer), for example, a polymer having a halogen group at the end of the polymer obtained by polymerizing a radically polymerizable monomer by the polymerization catalyst composition of the present invention, other than the polymerization catalyst composition of the present invention A polymer having a halogen group at an end obtained by polymerizing a radically polymerizable monomer with a living radical polymerization catalyst (composition) of the present invention, for example, different from the polymerization method of the present invention such as free radical polymerization, condensation polymerization, coordination polymerization A polymer obtained by modifying a part of the polymer obtained by the polymerization reaction with an organic halide can be mentioned.

Further, as the organic halides used in the present invention, for example, as shown in the formula (3), FeBr (A) and a thermal radical initiator 2,2′-azobisisobutyal-tolyl (described below) ,

3

 In the combination (abbreviated as AIBN) (B), a radical (C) formed by thermally cleaving AIBN (B) produces an FeBr force which also generates a bromine atom, such as an organic halide (E).

 3

 Also included are radicals formed by radical decomposition of a radical initiator that generates radicals by heat or light, and organic halides produced as a result of migration of halogen atoms from a transition metal halide.

[Formula 5] twenty three)

Among these organic halides, preferred are halogenated hydrocarbons, halogenated sulfonyls, halogenated carboxylic acid esters, halogenated nitriles, or halogenated ketones, and more preferable. Are halogenated hydrocarbons, a halogenated carboxylic acid esters, halogenated sulfonyls, and _a halogenated ditolyls, more preferably α halogenated carboxylic acid esters.

 «Transition Metal-Containing Phosphate-Comm Composition and Method of Preparing Polymerization Catalyst Composition» The transition metal-containing phosphat-comb composition of the present invention is a phosphazene compound represented by the above general formula (1) It can be prepared by mixing with the transition metal compound represented by the above general formula (2). In addition, the polymerization catalyst composition for a radically polymerizable monomer of the present invention can be prepared by mixing the transition metal-containing phosphate composition with the above-mentioned organic halide. The mixing method is not particularly limited, and conventionally known mixing methods can be applied.

 [0075] The transition metal-containing phosphaz- um composition is a mixture of the phosphaz- um compound and the transition metal compound, and a part or all of the composition is the phosphaz- um compound and the transition. It may be in the form of a reaction product with a metal compound (transition metal-containing phosphazene compound).

 << Production Method of Polymer >>

 The method for producing the polymer of the present invention is characterized by (co) polymerizing a radically polymerizable monomer using the polymerization catalyst composition of the present invention.

<< Radically Polymerizable Monomer >>

Examples of the radically polymerizable monomer used in the method of the present invention include all monomers in which the polymerization proceeds by a radical polymerization reaction. Specific examples of such radically polymerizable monomers include linear or branched olefins having 2 to 30 carbon atoms, such as ethylene, propylene, isobutylene and 1-nitrone, and examples thereof include cyclohexene, Cyclic olefins having a carbon number of 3 to 30, such as cyclopentadiene, for example, dienes such as butadiene, 1,5 hexazine, 1,3 octadiene, etc., for example, acrylic acid, methacrylic acid, etc. (Meth) acrylic acids, for example, methyl atalylate, Chill meta tarylate, ethyl atalylate, propyl meta tarylate, butyl atalylate, 2 cetyl hexyl meta tarylate, lauryl atalylate, stearyl meta tarylate, 2, 2, 2-trifluorethil atalylate, 2 2, 2-Trifluroethyl metatarylate, 1H, 1H, 2H, 2H-Heptadeca fluoro decyl atalylate, aryl atalylate, aryl meta tarylate, 2-methoxy ethyl atalylate, 2-ethoxy Ethyl methacrylate, 1-methoxy-2-propyl methacrylate, methoxydiethylene glycol atalylate, ethylene glycol diazatalylate, propylene glycol dimetatalylate, 1,3 propane diol dimetatalylate, neopentyl glycol diatalylate, glycerin Tria Tarylate, Linear or branched (meth) acrylic esters having 4 to 30 carbon atoms, such as triethylene glycol dimetatalylate, 2-dimethylaminoethyl atalylate, 2-ethylpropyl aminoethyl methacrylate, etc. For example, cyclic (meth) acrylic acid having a carbon number of 6 to 30 such as cyclohexyl methacrylate atalylate, tetrahydrofulfino linaliate, glycidyl atalylate, glycidyl methacrylate, 2-dicyclopente-l-oxetyl atalylate, etc. Esters, for example, benzyl atalylate, β-phenylethyl methacrylate, 2-phenyloxy atarylate, phenoxydipropylene glycol methacrylate, 2-benzoxyl atalylate Etc. (Meth) acrylic esters with aromatic rings of 9 to 30 carbon atoms, such as For example, (meth) ataryl groups such as acrylonitrile and methacrylonitrile; for example, acrylamide, methacrylamide, メ チ ル -methyl acrylamide, ブ チ ル -butyl acrylamide, ォ -octyl acrylamide, Ν, ジ メ チ ル -dimethyl acrylamide, Linear or branched (meth) acrylamides having 3 to 30 carbon atoms such as Ν, Ν, エ チ レ ン, Ν, ー, ジ ェ, ジ ェ, ジ ェ, エ チ レ ン, エ チ レ ン, エ チ レ ン, 例, glycidyl, for example; And cyclic (meth) acrylamides having 6 to 30 carbon atoms such as acrylamide, Ν, Ν diglycidyl acrylamide, Ν- atarilic piperidine, Ν- ataryloyl morpholine, and examples thereof include Ν phenyl acrylamide, Ν, Ν, -Ruacrylamide, 1-atariroylimi (Meth) acrylamides having an aromatic ring having a carbon number of 9 to 30, such as azoles, for example, bulidines such as 2 bul pyridine, 2 isopropyl pyridine, 4 bul pyridine, etc., for example, maleimide, Aliphatic (not) substituted maleimides such as Ν-methyl maleimide, Ν-cyclic hexylmaleimide, etc., for example, Ν- N-aromatic substituted maleimides such as maleimide, N- (4-methylphenyl) maleimide, etc., for example, methyl vinyl ketone, isopropyl methyl ketone, ethyl vinyl ketone

Straight-chain or branched vinyl ketones having 4 to 30 carbon atoms such as isobutyl isopropyl ketone and butyl vinyl ketone, and examples thereof include: cyclohexyl vinyl ketone; 2-cyclohexyl methyl ketone; cyclic of 5 to 30 carbon atoms And vinyl substituted ketones such as phenyl substituted ketones, such as styrene, m-methylstyrene, p-methylstyrene, p-t-butylstyrene, and p-bromo. C 8-30 substituted or unsubstituted styrenes such as styrene, p-methoxycarbonylstyrene, p-trifluoromethylstyrene, p-t-butoxycarbonylstyrene, p-cyanostyrene, etc. 1-Vinino Lef enanthrene, 2-Vinino Leanthracene, 2-Vinno Lefu Lulanthene, 2-Buer Naphtacene, 2-Vue Aromatic Bulle of compounds such as trinaphthylene, for example, 3 Byurufuran, 3 bi - Le thiophene, 2 Bulle pyrimidine

Aromatic heterocyclic compounds such as 2 vinyl quinoline, 3 vinyl naphthyridine, 3 vinyl indole, 3 vinyl pyrazole 4-bul pyrrole, 4-bul isoxazole, 5-bul indoline and the like, and examples thereof include maleic anhydride, 1-Cyclopentene 1,

2 Unsaturated carboxylic acid anhydrides such as dicarboxylic acid anhydride, citraconic acid anhydride, 2,3 diphenyl maleic acid anhydride, acrylic acid anhydride, methacrylic acid anhydride etc. Group carboxylic acid boule esters such as benzoic acid boule and the like, and aromatic carboxylic acid boule esters such as benzoic acid boule and the like.

 [0077] Among these radically polymerizable monomers, (meth) acrylic esters, (meth) ataryl tolyl, (meth) acrylamides, bipyridines, N-substituted maleimides, biketones and styrenes It is preferably used, and (meth) acrylic esters, styrenes and the like S are more preferably used.

 In the method for producing the polymer of the present invention, as long as the polymerization reaction is carried out in the presence of the polymerization catalyst composition of the present invention, these radical polymerizable monomers may be polymerized alone, or a plurality of monomers may be copolymerized. You may.

In the case of copolymerization, a method of simultaneously using a plurality of radically polymerizable monomers, a method of sequentially using, or a method of repeatedly using a method of sequentially using, etc. Can be taken. When two or more radically polymerizable monomers are simultaneously used in combination, depending on the difference in reactivity of the compounds, random copolymers are obtained. When two or more monomers are sequentially polymerized, A block copolymer comprising two or more blocks is obtained

The weight-average molecular weight Z number-average molecular weight (MwZMn) of the polymer obtained by the polymer production method of the present invention is not particularly limited, but is usually 2.0 or less, more preferably 1.7 or less More preferably, it is 1.5 or less.

 The type of polymerization reaction in the method of the present invention is not particularly limited. In general, a transition metal-containing phosphaz- um composition obtained by mixing the phosphaz- um compound and the above-mentioned transition metal compound under an atmosphere of an inert gas such as nitrogen or argon, and an organo, rogen compound, In the presence of the polymerization catalyst composition for radically polymerizable monomers containing the radically polymerizable monomers, the radically polymerizable monomers are mixed, and if necessary, the temperature is raised to a predetermined temperature in a solution in which these are dissolved in a suitable solvent. Carry out polymerization. The production method may be a batch method in which the above-described components are collectively fed, or a method in which radically polymerizable monomers are intermittently or continuously supplied. In addition, in the case of obtaining a copolymer, a method of intermittently or continuously supplying a plurality of radically polymerizable monomers simultaneously or collectively or a plurality of radically polymerizable monomers sequentially according to a desired copolymer. The method of supply can be taken.

[0080] Although not particularly limited amount of the transition metal compound, usually, of the radical polymerizable monomer 1 mole of using a ¹ X 10- ⁷ ~5 X 10- 1 mol, preferably, 1 X 10- ⁴ a to 3 X 10- ¹ mol, more preferably in the range of 5 X 10- ⁴ ~1 X 10- ¹ mol. The amount of the phosphite compound used is usually not less than 0.05 mol, preferably 0.5 to 6.0 mol, and more preferably 0.2 mol per mol of the transition metal compound. It is 95-4. 00 mol. The amount of the organic halide used can be suitably set according to the molecular weight of the polymer to be produced. Usually, 1 × 10 ′ ′ ^{4 to} 5 × 10−1 mol is preferable to ¹ mol of the radically polymerizable monomer, and it is preferable is a 5 X 10- ⁴ ~2 X 10- ¹ mol, more preferably from ¹ X 10- ³ ~1 X 10- 1 mol.

The temperature of the polymerization reaction can be appropriately set depending on the kind and amount of the phosphazem compound, transition metal compound, organic halogen compound and radically polymerizable monomer used, Usually, it is 0 ° C to 250 ° C, preferably in the range of 20 ° C to 150 ° C. The pressure of the polymerization reaction can be appropriately set depending on the type and amount of the radically polymerizable monomer to be used, the reaction temperature, etc., but is usually 3. OMPa (absolute pressure in terms of meganocle, hereinafter the same) or less. 0.10 to 1: L 5 MPa, more preferably 0.1 to 1. O MPa.

 The reaction time of the polymerization reaction depends on the reaction temperature and the like, such as the type and amount of the phosphazene compound, transition metal compound, initiator and radically polymerizable monomer to be used, but it is usually within 50 hours, preferably 0. 1-24 hours.

 The polymerization reaction in the process of the present invention can be carried out without solvent. If necessary, an appropriate solvent can be used. In some cases, the reaction solution may be homogeneous or suspended.

 The solvent is not particularly limited as long as it does not inhibit the present invention, and, for example, hydrocarbons, aromatic halides, ethers, aprotic polar solvents, alcohols or Water etc. are mentioned.

As the hydrocarbons, for example, aliphatic hydrocarbons having 5 to 30 carbon atoms such as n-hexane and n-heptane, for example, alicyclic hydrocarbons having 5 to 30 carbon atoms such as cyclohexane and the like For example, aromatic hydrocarbons having 6 to 30 carbon atoms such as benzene, toluene or xylene can be mentioned. Examples of the aromatic halides include aromatic halides having 6 to 30 carbon atoms such as, for example, benzene of benzene or dichlorobenzene. As the ethers, for example, aliphatic ethers having 2 to 30 carbon atoms such as jetyl ether, for example, alicyclic ethers having 10 to 30 carbon atoms such as dicyclohexyl ether, for example, diethyl ether And C12-C30 aromatic ethers, for example, tetrahydrofuran, tetrahydropyran, C3-C30 cyclic ethers such as 1,4-difluoroxan, for example, ethylene glycol dimethyl ether or diethylene glycol jetyl ether. Etc. The C3-C50 polyethers, etc., etc. are mentioned. Examples of the aprotic polar solvent include aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, sulfolane or N, N'-dimethylimidazolidinone. Examples of alcohols include aliphatic alcohols having 1 to 30 carbon atoms such as methanol, ethanol and propanol, alcohols having an aromatic ring having 6 to 30 carbon atoms such as benzyl alcohol and the like, for example phenol and taresol Aromatic hydroxylated with 6 to 30 carbon atoms Compounds etc. are mentioned. These solvents may be used alone or in combination of two or more.

 The polymerization method can be carried out by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, V, or any other method, and any other polymerization method may be used as long as the effects of the present invention are not impaired. I do not know.

 Although the polymer obtained by the method of the present invention may be used without purification, it is usually purified by a conventional polymer purification method such as reprecipitation, solvent evaporation, residual monomer evaporation and the like. Furthermore, in order to remove the polymerization catalyst composition used in the method of the present invention, in addition to these purification methods, for example, a polymerization catalyst such as activated carbon, alumina adsorbent, silica adsorbent or ion exchange resin etc. A method of adsorbing the composition, a method of extracting the polymerization catalyst composition in a dilute mineral acid aqueous solution, and the like may be combined as appropriate.

 << Polymer >>

 The polymer of the present invention is a polymer obtained by (co) polymerizing a radically polymerizable monomer using the polymerization catalyst composition of the present invention. The structure of the polymer of the present invention is not particularly limited, and homopolymers, random copolymers, graft copolymers, block copolymers, gradient copolymers, star polymers, comb polymers and the like can be exemplified.

 [Example]

 The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention.

In the following, all operations were performed under a dry nitrogen atmosphere unless otherwise noted. The solid reagent was weighed in a nitrogen-replaced glove box and charged into the reactor. The liquid reagent was collected by a container syringe and added to the reaction system. The solvent and radically polymerizable monomer were purified by distillation or column chromatogram if necessary. The radically polymerizable monomer and the solvent were nitrogen purged for at least 30 minutes before use. The conversion ratio of each monomer was calculated by performing quantitative analysis by gas chromatography using an internal standard substance. The number average molecular weight (Mn) and the molecular weight distribution (MwZMn) of the produced polymer were analyzed using GPC using tetrahydrofuran as a developing solvent. n-Butyl atarilate (nBA) and styrene (St) were analyzed by GPC using polystyrene as a standard substance . For methyl methacrylate (MMA), GPC analysis was performed using polymethyl methacrylate as a standard substance. The random and block copolymers of MMA and nBA were subjected to GPC analysis using polystyrene as a standard substance.

 [Abbreviation]

 PZNC1: tetrakis [tris (dimethylamino) phosphora-redaminoamino] phospho

Nim chloride: [(Me N) P = N] P ⁺ , CI-(Me is a methyl group

 2 3 4

 Represents And so on)

 PZNBr: tetrakis [tris (dimethylamino) phosphora-ideneamino] phospho

 -Um bromide: [(Me N) P = N] P +, Br-

 2 3 4

 PZNI: tetrakis [tris (dimethylamino) phosphoranylideneamino] phospho

You are here: [(Me N) Ρ = Ν] Ρ ⁺ , Γ

 2 3 4

 ΡΖΝ (OAc): tetrakis [tris (dimethylamino) phosphora-redaminoamino]

 Phosphonium acetate: [(Me N) P = N] P +, —OAc

 2 3 4

 (OAc represents an acetoxy group, and so forth)

EBP: 2-bromo ethyl propionate

EBIB: Ethyl 2-bromoisobutyrate

BEB: (1-Broochetinole) Benzene

nBA: Normal butyl acrylate

MMA: methyl methacrylate

St: styrene

Mn: number average molecular weight

Mw: weight average molecular weight

MwZMn: Molecular weight distribution

Mn: Theoretically calculated number average molecular weight

 , th

 Mn = Mwi + (Mm / Mi) X Mwm X (x / 100)

 , th

 Mm: number of moles of the radically polymerizable monomer charged

Mi: number of moles of organic halide charged

Mwi: Molecular weight of organic halide Mwm: Molecular weight of radically polymerizable monomer

 X: Conversion rate of radically polymerizable monomer (%)

 Example 1

 (Bulk polymerization of normal butyl acrylate (nBA) using PZNCl / FeBr)

 2

 In a nitrogen-substituted Schlenk reaction tube, 109 mg (0.14 mmol) of tetrakis [tris (dimethylamino) phosphora-ideneamino] phosphorus chloride (PZNCl), which is a phosphazene compound, and iron bromide (Π) which is a transition metal compound. 30. 2 mg (0.14 mmol) is precisely weighed and mixed, and then, using a syringe, 3.58 g (27.9 mmol) of nBA, which is a radically polymerizable monomer, and ethyl 2-bromopropionate (EBP) as an initiator 18. 1 ^ 1 (0.14 mmol), 0.2 ml of tridecane as an internal standard for gas chromatography determination, and stirring at room temperature for several minutes. Thereafter, the reaction mixture was heated and stirred at 90 ° C. for 2 hours to carry out a polymerization reaction. After completion of the reaction, the reaction product was cooled to 0 ° C. to terminate the polymerization. The conversion ratio of nBA was 85. 1%, the number average molecular weight (Mn) of the produced polymer was 19,300, and the molecular weight distribution (MwZMn) was 1.88. Theoretical molecular weight Mn calculated from conversion of nBA is 21900,

 , th

 The polymers Mn and Mn were close.

 , th

 Example 2

 (Bulk polymerization of nBA using PZNCl / FeBr)

 2

 Reaction and post-treatment as in Example 1 except using 55.3 mg (0. 07 mmol) of PZNC1 and 15. 1 mg (0. 07 mmol) of iron (II) bromide and changing the polymerization time to 4 hours I took care of it.

 The conversion ratio of nBA was 38.3%, the number average molecular weight (Mn) of the produced polymer was 10400, and the molecular weight distribution (MwZMn) was 1.41. Mn calculated from nBA conversion is 10000

 , th

 is there. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 3

 (Bulk polymerization of nBA using PZNCl / FeBr)

 2

The reaction and work-up were carried out in the same manner as in Example 2 except that 109 mg (0.14 mmol) of PZNC1 was used. The conversion ratio of nBA was 70.0%, the number average molecular weight (Mn) of the produced polymer was 15,600, and the molecular weight distribution (MwZMn) was 1.64. Mn calculated from nBA conversion is 18100

 , th

 is there. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 4

 (Bulk polymerization of nBA using PZNCl / FeBr)

 2

 The reaction and work-up were carried out in the same manner as in Example 2 except that 9.04 g (70.5 mmol) of nBA was used.

 The conversion of nBA was 23.5%, the number average molecular weight (Mn) of the produced polymer was 14100, and the molecular weight distribution (MwZMn) was 1.4. Mn calculated from nBA conversion is 15400

 , th

 is there. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 5

 (Use of PZNl / FeBr, bulk polymerization of nBA)

 2

 The reaction and work-up were carried out in the same manner as in Example 2 except that 60.7 mg (0.07 mmol) of PZNI was used instead of PZNC1.

 The conversion ratio of nBA was 47.7%, the number average molecular weight (Mn) of the produced polymer was 10300, and the molecular weight distribution (MwZMn) was 1.25. Mn calculated from nBA conversion is 12400

 , th

 is there. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 6

 (PZNl / FeBr is used for bulk polymerization of nBA)

 2

 The reaction and post treatment were carried out in the same manner as in Example 5 except that 121 mg (0.14 mmol) of PZNI was used and polymerization was carried out for 6 hours.

 The conversion ratio of nBA was 83.3%, the number average molecular weight (Mn) of the produced polymer was 19,500, and the molecular weight distribution (MwZMn) was 1.18. Mn calculated from nBA conversion is 21500

 , th

is there. The molecular weight distribution of the polymer produced is close to the theoretical value. A polymer with a narrow molecular weight distribution is obtained. Comparative Example 1

 (Bulk polymerization of nBA using phosphazene compounds)

 The reaction and the post-treatment were carried out in the same manner as in Example 1 except that no phosphaZene compound Was used. The conversion rate of nBA was 0% and no polymer was obtained.

 The polymerization did not proceed at all unless the phosphazene compound was used.

Comparative Example 2

 (Bulk polymerization of nBA using ammonium salt ZFeBr)

 2

 The reaction and the post-treatment were carried out in the same manner as in Example 1 except that tetrabutyl ammonium chloride was used instead of the phosphazene compound and polymerization was carried out for 8.5 hours.

 The conversion rate of nBA was 16.2%, and the polymerization reaction was very slow as compared with the case of using phosphazene compounds. The number average molecular weight (Mn) of the resulting polymer was 5300, and the molecular weight distribution (MwZMn) was 1.39. Mn calculated from nBA conversion is 4300

 , th Example 7

 (Bulk Polymerization of Styrene (St) Using PZNCl / FeBr)

 2

 PZNC167. 8mg (0. 0875mmol), iron bromide (1) 18.9mg (0. 0875mmol) was purified and mixed in a nitrogen-purged Schlenk reaction tube, and then a syringe was used! St3. 64 g (3. 49 mmol), BEB 23. 8 (0.17 mmol), 0.2 ml of o-xylene as an internal standard for gas chromatography determination were added, and the mixture was stirred at room temperature for several minutes. Thereafter, the reaction mixture was heated and stirred at 110 ° C. for 4 hours to carry out a polymerization reaction. After completion of the reaction, the reaction product was cooled to 0 ° C. to terminate the polymerization.

The conversion of St was 49.8%, the number average molecular weight (Mn) of the produced polymer was 9,700, and the molecular weight distribution (MwZMn) was 1.14. Mn calculated from the conversion of St is 10,300

 , th

 . The molecular weight distribution of the produced polymer is close to the theoretical value. A narrow molecular weight distribution is also obtained Example 8

 (PZNl / FeBr used, bulk polymerization of St)

 2

Except for using 75.8 mg (0. 0875 mmol) of PZNI instead of PZNC1, all the results are real. The reaction and work-up were carried out as in Example 7.

 The conversion of St was 38.9%, the number average molecular weight (Mn) of the produced polymer was 6,800, and the molecular weight distribution (MwZMn) was 1.13. The Mn calculated from the conversion of St is 8300.

 , th

 The molecular weight distribution of the produced polymer was close to the theoretical value and a narrow molecular weight distribution was obtained. Example 9

 (Bulk polymerization of methyl methacrylate (MMA) using PZNCl / FeBr)

 2

 PZNC 183. Omg (0. 107 mmol), iron bromide (Π) 23. Omg (0. 107 mmol) are precisely mixed in a Schlenk reaction tube purged with nitrogen, and then mixed using a syringe. 40. 9 mmol), EBIB 31.7 ^ 1 (0.213 mmol), 0.2 ml of tridecane as an internal standard for gas chromatography determination, and the mixture was stirred at room temperature for several minutes. Thereafter, the reaction mixture was heated and stirred at 70 ° C. for 4 hours to carry out a polymerization reaction. After completion of the reaction, the reaction product was cooled to 0 ° C. to terminate the polymerization.

 The conversion rate of MMA was 48.5%, the number average molecular weight (Mn) of the resulting polymer was 9,500, and the molecular weight distribution (MwZMn) was 1.45. Mn calculated from MMA conversion is 9500

 , th

 is there. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 10

 (Solution polymerization of MMA using PZNCl / FeBr)

 2

 PZNC172. 5 mg (0.00935 mmol) and iron (II) bromide 20. 2 mg (0.00935 mmol) are precisely mixed and mixed in a nitrogen-purged Schlenk reaction tube, and then, using a syringe, MMA 3. 66 g (36. 6 mmol), EBIB 27. 8 ^ 1 (0. 187 mmol), o-xylene (4 ml) as solvent, 0.2 ml of tridecane as internal standard for gas chromatography determination and stirring for several minutes at room temperature did. A small amount of pre-polymerization sample was withdrawn from the solution and analyzed for MMA. Thereafter, the reaction mixture was heated and stirred at 80 ° C. for 4 hours to carry out a polymerization reaction. After completion of the reaction, the reaction product was cooled to 0 ° C. to terminate the polymerization.

The conversion rate of MMA was 49.6%, the number average molecular weight (Mn) of the produced polymer was 9,600, and the molecular weight distribution (MwZMn) was 1.47. Mn calculated from conversion of MMA is 9900

 , th

is there. The molecular weight distribution of the polymer produced is close to the theoretical value. A polymer with a narrow molecular weight distribution is obtained. It was

 Example 11

 (Solution polymerization of MMA using PZNl / FeBr)

 2

 The reaction and work-up were carried out in the same manner as in Example 10 except that 81. Omg (0. O935 mmol) of PZNI was used instead of PZNC1.

 The conversion ratio of MMA was 64. 8%, the number average molecular weight (Mn) of the resulting polymer was 13200, and the molecular weight distribution (MwZMn) was 1.35. Mn calculated from MMA conversion is 1420

 , th

 It is 0. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 12

 (Solution polymerization of MMA using PZN (OAc) / FeBr)

 2

 The reaction and the post-treatment were carried out in the same manner as in Example 10 except that 74.7 mg (0.0935 mmol) of PZN (OAc) was used instead of PZNC1.

 The conversion rate of MMA was 45.7%, the number average molecular weight (Mn) of the resulting polymer was 11,400, and the molecular weight distribution (MwZMn) was 1.47. Mn calculated from conversion of MMA is 9300

 , th. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 13

 (Random copolymerization of MMA and nBA using PZNl / FeBr)

 2

In a nitrogen-purged Schlenk reaction tube, 121 mg (0.140 mmol) of PZNI and 30.2 mg (0.140 mmol) of iron bromide (Π) are precisely weighed and mixed, and then, using a syringe, nBA 3.68 g (28. 7 mmol), 2.65 g (26.5 mmol) of MMA, EBP 36.4 ^ 1 (0.28 mmol) as an initiator, 0.2 ml of tridecane as an internal standard for gas chromatography determination, and stirred at room temperature for several minutes. Thereafter, the reaction mixture was heated and stirred at 90 ° C. for 4 hours to carry out a polymerization reaction. After completion of the polymerization reaction, the reaction product was cooled to 0 ° C. to terminate the polymerization. The reaction product was diluted with tetrahydrofuran, and the polymerization catalyst composition was removed through a neutral alumina column, and then dropped into a water Z methanol mixed solvent to precipitate a polymer. The precipitated polymer was filtered and dried under reduced pressure to obtain a polymer as a white powder. The conversion rate of MMA was 74.4%, and the conversion rate of nBA was 41.6%. The number average molecular weight (Mn) of the produced polymer was 10,800, and the molecular weight distribution (MwZMn) was 1.33. Transfer rate force of MMA and nBA The calculated Mn is 12700. Molecular weight of the formed polymer

 , th

 A polymer with a narrow molecular weight distribution close to the theoretical value was obtained.

In addition, when ¹ H-NMR of the obtained polymer was measured, MMA and nBA were contained in the polymer at a molar ratio of 61Z39! /. The molar ratio in the polymer calculated from the conversion of MMA and nBA is MMAZnBA = 62Z38, and in the polymer of this example, MMA and nBA are contained in a ratio close to the theoretical value! /.

 Example 14

 (Block copolymerization of MMA and nBA using PZNl / FeBr)

 2

 PZNI60.7 mg (0. 07 mmol) and iron bromide (Π) 15.1 mg (0. 07 mmol) are precisely weighed and mixed in a nitrogen-substituted Schlenk reaction tube, and then the first monomer is prepared using a syringe. There were added nBA 3.53 g (27.5 mmol), EBP 18.2 ^ 1 (0.28 mmol), 0.2 ml of tridecane as an internal standard for gas chromatography determination, and the mixture was stirred at room temperature for several minutes. Thereafter, the reaction mixture was heated and stirred at 90 ° C. to carry out a polymerization reaction. One hour after the initiation of polymerization, a part of the reaction solution was taken out and analyzed. The conversion of nBA was 17.7%, the Mn of the produced polymer was 5400, and the MwZMn was 1.35. Further, 3.70 g (36.9 mmol) of MMA as a second monomer was added to this reaction solution, and polymerization was continued at 90 ° C. for 4 hours. After completion of the polymerization reaction, the reaction mixture was cooled to 0 ° C. to terminate the polymerization. The reaction product was diluted with tetrahydrofuran, and the polymerization catalyst composition was removed through a neutral alumina column, and then dropped into a mixed solvent of water and Z-methanol to precipitate a polymer. The precipitated polymer was filtered and then dried under reduced pressure to obtain a polymer as a white powder.

[0108] The conversion of MMA was 55.5%, and the conversion of nBA was 34.1%. The number average molecular weight (Mn) of the produced polymer was 28900, and the molecular weight distribution (MwZMn) was 1.3. Conversion force of MMA and nBA The calculated Mn is 23,600. Molecular weight of the formed polymer

 , th

 A polymer with a narrow molecular weight distribution close to the theoretical value was obtained.

Also, when ¹ H-NMR of the obtained polymer was measured, MMA and nBA were contained in the polymer in a molar ratio of 71/29! /, In the polymer. Calculated from conversion of MMA and nBA The molar ratio in the polymer was MMAZnBA = 69Z31, and in the polymer of this example, MMA and nBA were contained in a ratio close to the theoretical value! /.

 Example 15

 [0109] (Bulk polymerization of ΒΑ using PZNBr / FeCl · 4Ο)

 twenty two

 Use PZNBr 459. Omg (0.56 mmol) instead of PZNC1, iron chloride (Π) tetrahydrate 27.8 mg (0.14 mmol) instead of iron bromide (0), change the polymerization time to 6 hours The reaction and the post-treatment were carried out in the same manner as in Example 1 except for the above.

 The conversion rate of nBA was 33.7%, the number average molecular weight (Mn) of the produced polymer was 10100, and the molecular weight distribution (MwZMn) was 1.4. Mn calculated from nBA conversion is 8800

 , th

 is there. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 16

 (Bulk polymerization of nBA using PZNBr / FeBr 4ΗO)

 twenty two

 PZNBr 229. 5 mg (0.28 mmol) instead of PZNC1, iron bromide (.) Tetrahydrate 20. 1 mg (0.07 mmol) instead of iron bromide (Π), polymerization time is 6 hours The reaction and work-up were carried out in the same manner as in Example 1 except for the change.

 The conversion ratio of nBA was 65.7%, the number average molecular weight (Mn) of the produced polymer was 16,300, and the molecular weight distribution (MwZMn) was 1.45. Mn calculated from nBA conversion is 16900

 , th

 is there. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 17

 (Bulk polymerization of St using PZNClZFeBr)

 2

 PZNC1527. 2 mg (0. 68 mmol), iron bromide (II) 36.7 mg (0. 17 mmol) and St3 5. 4 g (340 mmol) were used, and all of the examples 7 were used except that the polymerization time was changed to 10 hours. The reaction and workup were carried out in the same manner as in.

 The conversion of St was 51.6%, the number average molecular weight (Mn) of the resulting polymer was 93,800, and the molecular weight distribution (MwZMn) was 1.50. The Mn calculated from the conversion of St is 107,700.

 , th

Ru. The resulting polymer has a molecular weight close to the theoretical value, and a narrow molecular weight distribution is obtained. The

 Example 18

 (Solution polymerization of MMA using PZNl / FeBr)

 2

 The reaction and work-up were carried out in the same manner as in Example 11 except that bromoacetonitrile 13.01 (0.183 mmol) was used instead of EBIB.

 The conversion ratio of MMA was 60.1%, the number average molecular weight (Mn) of the produced polymer was 12,800, and the molecular weight distribution (MwZMn) was 1.3. Mn calculated from MMA conversion is 1200

 , th

 It is 0. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Example 19

 (Solution polymerization of MMA using PZNl / FeBr)

 2

 The reaction and the post-treatment were carried out in the same manner as in Example 11 except that methanesulfoglycolide 14.5.1 (0.183 mmol) was used instead of EBIB.

 The conversion rate of MMA was 58.3%, the number average molecular weight (Mn) of the resulting polymer was 11,500, and the molecular weight distribution (MwZMn) was 1.38. Mn calculated from conversion of MMA is 1160

 , th

 It is 0. The molecular weight distribution of the produced polymer was close to the theoretical value, and a narrow molecular weight distribution was obtained.

 Industrial applicability

 According to the present invention, a polymerization catalyst composition for a radically polymerizable monomer excellent in living property and a living polymerizable polymer using the same can be obtained, and various industrial resin products can be provided.

Claims

[1] A phosphazene compound represented by the following general formula (1) and a compound of at least one transition metal selected from group 4 to 12 of the periodic table represented by the following general formula (2) Transition metal-containing phosphatase composition obtained by mixing.

 [Formula 1]

(Wherein, n is an integer of 1 or more and represents the number of phosphazeium cations, and Z ⁿ — is a form in which n protons having active hydrogen atoms having n active hydrogen atoms are separated and derived A, b, c and d are each a positive integer of 3 or less or 0, but not all 0 at the same time.

R ⁹ , R ^{1 Q} , R ¹

^{\ R 12, R 13, R} 14, R 15, R 16, R 17, R 18, R 19, R 2. And R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may be the same or different. Also, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁹ and R 1 ^Q , R ¹¹ and R ¹² , R ¹³ and R ^W , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁹ and R ² °, R ²¹ and R ²² , R ²³ and R ²⁴ may be bonded to each other to form a ring. )

 [Formula 2]

LpM ^{m +} ( ^r- ) _q (2)

(Wherein, L represents a neutral ligand, p represents the number of neutral ligands, and is an integer of 0 or 1 to 8) M is also a group 4 to 12 group power in the periodic table Is a transition metal, m is a valence number of the transition metal M, and is an integer of 1 to 8. Represents the form of ァ -on, q represents the number of オ ン -on, and is an integer of 1 to 8; r represents the valence of an electron and is an integer of 1 to 8. The relationship between m, r and q is represented by m = r x q. )

 [2] A polymerization catalyst composition for a radically polymerizable monomer, comprising the transition metal-containing phosphatase composition according to claim 1 and an organic halide.

[3] The polymerization catalyst composition according to claim 2, wherein all the groups in the general formula (1) to ⁴ are methyl groups.

 [4] The polymerization catalyst composition according to claim 2 or 3, wherein a, b, c and d in the general formula (1) are all 1.

[5] Z ⁿ — in the above general formula (1) is an ァ -on of a form in which the proton of the mineral acid is eliminated and derived

The polymerization catalyst composition according to any one of claims 2 to 4.

[6] The polymerization catalyst composition according to claim 5, wherein Z ⁿ — in the general formula (1) is a chloride ion, a bromide ion or an iodide ion.

[7] An active hydrogen compound in which Z ⁿ — in the general formula (1) has an active hydrogen atom on an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom to which an electron absorbing group is bonded. The polymerization catalyst composition according to any one of claims 2 to 4, which is in the form of anion derived from protons.

 [8] The transition metal is a transition metal of Groups 7, 8, 9, 10, or 11 of the periodic table.

The polymerization catalyst composition according to any one of claims 2 to 7.

[9] The polymerization catalyst composition according to claim 8, wherein the transition metal is copper or iron.

[10] The polymerization catalyst composition according to any one of claims 2 to 9, wherein the transition metal compound is a transition metal chloride, bromide or iodide.

[11] The organic halide power: halogenated hydrocarbons, halogenated sulfonyls, ex-halogenated carboxylic acid esters, _a halogenated-tolyl compounds or di-halogenated ketones, [2]: L0: The polymerization catalyst composition as described in any one of the above.

[12] A method for producing a polymer, comprising (co) polymerizing a radically polymerizable monomer in the presence of the polymerization catalyst composition according to any one of claims 2 to 11.

[13] Said radically polymerizable monomer force (meth) acrylic acid esters, (meth) acrylonitrile The method for producing a polymer according to claim 12, wherein the polymer is selected from the group consisting of (meth) acrylamides, burepyridines, N-substituted maleimides, bureketones, and styrenes.

 [14] The method for producing a polymer according to claim 12 or 13, wherein the weight average molecular weight Z number average molecular weight of the obtained polymer is 2.0 or less.

 [15] A polymer obtained by the method for producing a polymer according to any one of claims 12 to 14.